Azodyestuffs insoluble in water and fiber dyed therewith



Patented June 20, I933 airs TES

LEOPOLD LASKA AND ARTHUR ZITSCHER,

0F OFFENBACH-ON-TEE-IVIAIN, GERMANY,

ASSIGNORS TO GENERAL ANILINE 'WORKS, INC., 0.? NEW YORK, N. Y., A OORPOR-A- TION OF DELAWARE .AZODYESTUFFS INSOLUBLE IN WATER AND FIBER DYED THEREWITH No Drawing. Application filed August 17, 1931, Serial No. 557,724, and in Germany August 19, 1930.

Our present invention relates to new azo' dyestuffs insoluble in water and to fiber dyed therewith.

These dyestuffs correspond probably to the general formula:

-alkylamino-sulfonyl-groups andn means the number 1 or 2.

They are prepared by diazotizing monoamino-5.(i-benzo-carbazole (described in Berichte der deutschen chemischen Gesellschaft, vol. 46, page 3723) and combining the diazo compound thus formed with a Q-hydroXy naphthalene 3-carbonyl-amino-aryl (wherein aryl means the aromatic radical signified in the above formula by or a corresponding di (2 hydroxy naphthalene 8- carbonyl-amino) -aryl.

The monoamino-5.6-benzo-carbazole used as diazo-component in the production of our new dyestuffs has, according to the above reference, the constitution of 3-amino5.6-benzocarbazole. Throughout this specification and the claims we use this alleged constitution. As, however, no proof for this assumption is given in the said reference and we do not know any argument warranting it, we use it without guaranty and write therefore (3) -amin0-5.G-benzo-carbazole and give the structural formulae as probably corresponding to our dyestuffs.

tinguished by a very good fastness to chlo- In order to further illustrate our invention, the following examples are given; we wish it however to be understood that we are not limited to the particular products or reaction conditions mentioned therein:

Example 1 Well boiled and dried cotton yarn is im pregnated with a solution containing per liter &' grs. of l- (Q-hydroxy-naphthalene-3-carbonyl)-amino-naphthalene, 12 c.c. of caustic soda solution of 34 B. and 10 c.c. of Turkey red oil. The goods are well wrung out, developed in a solution containing per liter the diazo compound of 2.3 grs. of (3)- amino-5.6-benZo-carbazole and being neutralized with sodum bicarbonate, rinsed and soaped. I

In this manner a reddish dark blue dyeing, of a very good fastness to chlorine and to boiling is obtained. The dyestuff thus produced on the fiber corresponds probably to the following formula: I

Ewample 2 Cotton yarn, previously treated in a suitable manner, is impregnated with a solution containing per liter 5.5 grs. of 1-(2-hydroxynaphthalene-S-carbonyl) -amino3-methyl-4- methoxybenzene, 11 cc. of caustic soda solution of 34 B. and 10 cc. of Turkey red oil. The goods are well dehydrated and developed in a solution which contains per liter the diazo compound of 2.3 grs. of (3) -amino- 5.6-benzo-carbazole. After finishing in the usual manner a dark blue dyeing of a very good fastness to chlorine and to boiling is obtained.

The dyestufi thus produced on the fiber corresponds probably to the formula:

The following table shows the shades of some other combinations of this type:

The same diazo compound yields on cotton with the (2 hydroxy naphthalene 3 carb0nyl)-compound of:

Shades -Amino-benzene Reddlsh dark blue -2-amino-napbthalene'. Blackish blue -l-amino-2-methyl-benzene Reddish dark blue -l-amino4cl1loro-benzene Dark blue -1-arnino-2-methyl-5-chloro-benzene Greenish dark blue -1-amino-4-chloro-2.adimethoxy benzene Dark blue -l-amino-2-methoxy-benzene Reddish dark blue -1-amino-2-ethoxy-benzene D ark blue -l-amin0-3chloro-benzene Reddish dark blue '-1-amino-2.fi-dimethoxy-benzene D ark blue -1-a.mino-2-methoxy-4-chloro-benzene. Do. -1-amino-2-methyl+chloro-benzene Do. -barnino--methoxy-naphthalene Do. -1-amin0-3-chlore-2.4-dimetl1oxy-benzene Do. -1-axnino-4-bromo-2.adimethoxy-benzene Do. -2-amino-3-methoxy-naphthalene D 0.

-4 amino-acenaphtliene Reddish dark blue -2'aminocarbazole- Dark blue Juminoantliracene. Greyish blue -(3-amino-benzoyl-amino)-benzene Greenish blue -l-amino-3.4dichloro-benzene Reddish blue 6-amino-2-methyl-quinoline Navy blue -1-amino-3-(dimethyl-amino-sulfonyl)-benzene Greenish blue -1-amino-2-methyl5-(ethyl-sullonyl)-benzene Do.

Ewample 3 A solution containing 4 grs. of 1-(2-hydroxy naphthalene-3-carbonyl) amino 4:-

methoxy-benzene, 12 cc. of caustic soda solutionof 34 136,20 do of Turkey red oil and one of the usual silk-protecting agents, for instance sulfite-cellulose waste liquor, is made up to 1 liter.

In this padding solution a silk hank is impregnated at 25 C. for 15 minutes. Then the bath is mixed with 10 grs. of common salt. The hank is again handled for a quarter of an hour and then well dehydrated.

The hank thus impregnated is developed in a solution which contains per liter the diazo compound of 2.3 grs. of (3) -amino- 5.6-benzo-carbazole and which is neutralized with sodium acetate and then mixed with 5 cc. of an acetic acid of 50% strength and 10 grs. of common salt per liter. After rinsing and soaping a blue dyeing is obtained.

The dyestufi' thus produced on the fiber corresponds probably to the formula:

The same diazo compound yields with 4;.l'-di- (Q-hydroxy naphthalene-3-carbonylamino) -3.3-dimethoxy-diphenyl a reddish blue dyeing.

On wool, the same diazo compound yields with 2- (2-hydroxy-naphthalene-3-carbonyl) amino-naphthalene a greylsh blue dyeing.

Ewample J,

Viscose is impregnated in a bath containing per liter 3 grs. of 1- (Q-hydroxy-naphthalene-3-carbonyl) -amino-3-nitro-benzene, 6 0.0. of caustic soda solution of 3 B. and

20 0.0. of Turkey red oil. After half an hour the goods are well centrifuged and developed in a solution which contains per liter the diazo compound of 2.3 grs. of (3) -amino-5.6-benzocarbazole and whereof the excess of mineral acid is neutralized with sodium acetate.--

' The same diazo compound yields with 1- (2-hydroXy-naphthalene-3-carbonyl) -aminonaphthalene a reddish blue dyeing.

'We claim:

I. As new compounds the azodyestufi's corresponding probably to the general formula:

wherein R means an aromatic radical of the benzene, naphthalene, anthracene, acenaphhem wherein R means a benzene radical which may be substituted by alkyl, alkoxy, halogen, nitro-, phenylamino-carbonyl-, alkyl-sulfonyl-, or dialkylamino-sulfonyl-groups.

3. As a new compound the azodyestuff corresponding probably to the formula:

which compound is insoluble in water and yields when produced on fibers reddish dark blue shades of a good fastness to chlorine.

4. As a new compound the azodyestufif corresponding probably to the formula:

which compound is insoluble in water and yields when produced on fibers dark blue shades of a good fast-ness to chlorine.

5. Fiber dyed with the azodyestufi's as claimed in claim 1.

6. Fiber dyed with the azodyestufls as claimed in claim 2.

7. Fiber dyed With the azodyestuff as claimed in claim 3.

8. Fiber dyed with the azodyestuff as claimed in claim 4.

In testimony whereof we affix our signatures.

LEOPOLD LASKA. ARTHUR ZITSCHER. 

